Zeolite SSZ-47

ABSTRACT

The present invention relates to new crystalline zeolite SSZ-47 prepared using a bicyclo ammonium cation templating agent.

This application claims priority from U.S. provisional application Ser.No. 60/034,461, filed Dec. 31, 1996.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new crystalline zeolite SSZ-47, amethod for preparing SSZ-47 using a selected group of bicyclo ammoniumcation templating agents, and processes employing SSZ-47 as a catalyst.

2. State of the Art

Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

Crystalline aluminosilicates are usually prepared from aqueous reactionmixtures containing alkali or alkaline earth metal oxides, silica, andalumina. Crystalline borosilicates are usually prepared under similarreaction conditions except that boron is used in place of aluminum. Byvarying the synthesis conditions and the composition of the reactionmixture, different zeolites can often be formed.

SUMMARY OF THE INVENTION

The present invention is directed to a family of crystalline molecularsieves with unique properties, referred to herein as "zeolite SSZ-47" orsimply "SSZ-47". Preferably, SSZ-47 is obtained in its silicate,aluminosilicate, titanosilicate, vanadosilicate or borosilicate form.The term "silicate" refers to a zeolite having a high mole ratio ofsilicon oxide relative to aluminum oxide, preferably a mole ratiogreater than 100. As used herein, the term "aluminosilicate" refers to azeolite containing both alumina and silica and the term "borosilicate"refers to a zeolite containing oxides of both boron and silicon.

In accordance with this invention, there is also provided a zeolitehaving a mole ratio greater than about 20 of an oxide of a firsttetravalent element to an oxide of a second tetravalent elementdifferent from said first tetravalent element, trivalent element,pentavalent element or mixture thereof and having, after calcination,the X-ray diffraction lines of Table II.

Further, in accordance with this invention, there is provided a zeolitehaving a mole ratio greater than about 20 of an oxide selected fromsilicon oxide, germanium oxide and mixtures thereof to an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, boron oxide, titaniumoxide, indium oxide, vanadium oxide and mixtures thereof and having,after calcination, the X-ray diffraction lines of Table II below.

The present invention further provides such a zeolite having acomposition, as synthesized and in the anhydrous state, in terms of moleratios as follows: ##EQU1## wherein Y is silicon, germanium or a mixturethereof; W is aluminum, gallium, iron, boron, titanium, indium, vanadiumor mixtures thereof; c is 1 or 2; d is 2 when c is 1 (i.e., W istetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W istrivalent or 5 when W is pentavalent); M is an alkali metal cation,alkaline earth metal cation or mixtures thereof; n is the valence of M(i.e., 1 or 2); and Q is at least one bicyclo ammonium cation.

In accordance with this invention, there is also provided a zeoliteprepared by thermally treating a zeolite having a mole ratio of an oxideselected from silicon oxide, germanium oxide and mixtures thereof to anoxide selected from aluminum oxide, gallium oxide, iron oxide, boronoxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereofgreater than about 20 at a temperature of from about 200° C. to about800° C., the thus-prepared zeolite having the X-ray diffraction lines ofTable II. The present invention also includes this thus-prepared zeolitewhich is predominantly in the hydrogen form, which hydrogen form isprepared by ion exchanging with an acid or with a solution of anammonium salt followed by a second calcination.

Also provided in accordance with the present invention is a method ofpreparing a crystalline material comprising an oxide of a firsttetravalent element and an oxide of a second tetravalent element whichis different from said first tetravalent element, trivalent element,pentavalent element or mixture thereof, said method comprisingcontacting under crystallization conditions sources of said oxides and atemplating agent comprising a bicyclo ammonium cation.

The present invention additionally provides a process for convertinghydrocarbons comprising contacting a hydrocarbonaceous feed athydrocarbon converting conditions with a catalyst comprising the zeoliteof this invention. The zeolite may be predominantly in the hydrogenform. It may also be substantially free of acidity.

Further provided by the present invention is a hydrocracking processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form.

This invention also includes a dewaxing process comprising contacting ahydrocarbon feedstock under dewaxing conditions with a catalystcomprising the zeolite of this invention, preferably predominantly inthe hydrogen form.

The present invention also includes a process for improving theviscosity index of a dewaxed product of waxy hydrocarbon feedscomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising the zeolite of thisinvention, preferably predominantly in the hydrogen form.

The present invention further includes a process for producing a C₂₀₊lube oil from a C₂₀₊ olefin feed comprising isomerizing said olefin feedunder isomerization conditions over a catalyst comprising at least oneGroup VIII metal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

In accordance with this invention, there is also provided a process forcatalytically dewaxing a hydrocarbon oil feedstock boiling above about350° F. and containing straight chain and slightly branched chainhydrocarbons comprising contacting said hydrocarbon oil feedstock in thepresence of added hydrogen gas at a hydrogen pressure of about 15-3000psi with a catalyst comprising at least one Group VIII metal and thezeolite of this invention, preferably predominantly in the hydrogenform. The catalyst may be a layered catalyst comprising a first layercomprising at least one Group VIII metal and the zeolite of thisinvention, and a second layer comprising an aluminosilicate zeolitewhich is more shape selective than the zeolite of said first layer.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one Group VIIImetal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

Further included in this invention is a process for isomerizationdewaxing a raffinate comprising contacting said raffinate in thepresence of added hydrogen with a catalyst comprising at least one GroupVIII metal and the zeolite of this invention. The raffinate may bebright stock, and the zeolite may be predominantly in the hydrogen form.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content comprising contacting a hydrocarbonaceous feedstockwhich comprises normal and slightly branched hydrocarbons having aboiling range above about 40° C. and less than about 200° C., underaromatic conversion conditions with a catalyst comprising the zeolite ofthis invention made substantially free of acidity by neutralizing saidzeolite with a basic metal. Also provided in this invention is such aprocess wherein the zeolite contains a Group VIII metal component.

Also provided by the present invention is a catalytic cracking processcomprising contacting a hydrocarbon feedstock in a reaction zone undercatalytic cracking conditions in the absence of added hydrogen with acatalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. Also included in this invention issuch a catalytic cracking process wherein the catalyst additionallycomprises a large pore crystalline cracking component.

This invention further provides an isomerization process for isomerizingC₄ to C₇ hydrocarbons, comprising contacting a feed having normal andslightly branched C₄ to C₇ hydrocarbons under isomerizing conditionswith a catalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. The zeolite may be impregnated withat least one Group VIII metal, preferably platinum. The catalyst may becalcined in a steam/air mixture at an elevated temperature afterimpregnation of the Group VIII metal.

Also provided by the present invention is a process for alkylating anaromatic hydrocarbon which comprises contacting under alkylationconditions at least a molar excess of an aromatic hydrocarbon with a C₂to C₂₀ olefin under at least partial liquid phase conditions and in thepresence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The olefin may be a C₂ toC₄ olefin, and the aromatic hydrocarbon and olefin may be present in amolar ratio of about 4:1 to about 20:1, respectively. The aromatichydrocarbon may be selected from the group consisting of benzene,toluene, ethylbenzene, xylene, or mixtures thereof.

Further provided in accordance with this invention is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The aromatic hydrocarbonand the polyalkyl aromatic hydrocarbon may be present in a molar ratioof from about 1:1 to about 25:1, respectively. The aromatic hydrocarbonmay be selected from the group consisting of benzene, toluene,ethylbenzene, xylene, or mixtures thereof, and the polyalkyl aromatichydrocarbon may be a dialkylbenzene.

Further provided by this invention is a process to convert paraffins toaromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising thezeolite of this invention, said catalyst comprising gallium, zinc, or acompound of gallium or zinc.

In accordance with this invention there is also provided a process forisomerizing olefins comprising contacting said olefin under conditionswhich cause isomerization of the olefin with a catalyst comprising thezeolite of this invention.

Further provided in accordance with this invention is a process forisomerizing an isomerization feed comprising an aromatic C₈ stream ofxylene isomers or mixtures of xylene isomers and ethylbenzene, wherein amore nearly equilibrium ratio of ortho-, meta- and para-xylenes isobtained, said process comprising contacting said feed underisomerization conditions with a catalyst comprising the zeolite of thisinvention.

The present invention further provides a process for oligomerizingolefins comprising contacting an olefin feed under oligomerizationconditions with a catalyst comprising the zeolite of this invention.

This invention also provides a process for converting lower alcohols andother oxygenated hydrocarbons comprising contacting said lower alcoholor other oxygenated hydrocarbon with a catalyst comprising the zeoliteof this invention under conditions to produce liquid products.

Also provided by the present invention is an improved process for thereduction of oxides of nitrogen contained in a gas stream in thepresence of oxygen wherein said process comprises contacting the gasstream with a zeolite, the improvement comprising using as the zeolite azeolite having a mole ratio greater than about 20 of an oxide of a firsttetravalent element to an oxide of a second tetravalent elementdifferent from said first tetravalent element, trivalent element,pentavalent element or mixture thereof and having, after calcination,the X-ray diffraction lines of Table II. The zeolite may contain a metalor metal ions (such as cobalt, copper or mixtures thereof) capable ofcatalyzing the reduction of the oxides of nitrogen, and may be conductedin the presence of a stoichiometric excess of oxygen. In a preferredembodiment, the gas stream is the exhaust stream of an internalcombustion engine.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a family of crystalline, large porezeolites designated herein "zeolite SSZ-47" or simply "SSZ-47". As usedherein, the term "large pore" means having an average pore size diametergreater than about 6.0 Angstroms, preferably from about 6.5 Angstroms toabout 7.5 Angstroms.

In preparing SSZ-47 zeolites, a bicyclo ammonium cation is used as acrystallization template. In general, SSZ-47 is prepared by contactingan active source of one or more oxides selected from the groupconsisting of monovalent element oxides, divalent element oxides,trivalent element oxides, and tetravalent element oxides with thebicyclo ammonium cation templating agent.

SSZ-47 is prepared from a reaction mixture having the composition shownin Table A below.

                  TABLE A                                                         ______________________________________                                                     Reaction Mixture                                                              Typical                                                                              Preferred                                                 ______________________________________                                        YO.sub.2 /W.sub.a O.sub.b                                                                    >30      30-40                                                 OH--/YO.sub.2  0.10-0.50                                                                              0.20-0.30                                             Q/YO.sub.2     0.05-0.50                                                                              0.10-0.20                                             M.sub.2/n /YO.sub.2                                                                          0.02-0.50                                                                              0.05-0.10                                             H.sub.2 O/YO.sub.2                                                                           20-80    30-45                                                 ______________________________________                                    

where Y, W, Q, M and n are as defined above, and a is 1 or 2, and b is 2when a is 1 (i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W istrivalent).

In practice, SSZ-47 is prepared by a process comprising:

(a) preparing an aqueous solution containing sources of at least oneoxide capable of forming a crystalline molecular sieve and a bicycloammonium cation having an anionic counterion which is not detrimental tothe formation of SSZ-47;

(b) maintaining the aqueous solution under conditions sufficient to formcrystals of SSZ-47; and

(c) recovering the crystals of SSZ-47.

Accordingly, SSZ-47 may comprise the crystalline material and thetemplating agent in combination with metallic and non-metallic oxidesbonded in tetrahedral coordination through shared oxygen atoms to form across-linked three dimensional crystal structure. The metallic andnon-metallic oxides comprise one or a combination of oxides of a firsttetravalent element(s), and one or a combination of a second tetravalentelement(s) different from the first tetravalent element(s), trivalentelement(s), pentavalent element(s) or mixture thereof. The firsttetravalent element(s) is preferably selected from the group consistingof silicon, germanium and combinations thereof. More preferably, thefirst tetravalent element is silicon. The second tetravalent element(which is different from the first tetravalent element), trivalentelement and pentavalent element is preferably selected from the groupconsisting of aluminum, gallium, iron, boron, titanium, indium, vanadiumand combinations thereof. More preferably, the second trivalent ortetravalent element is aluminum or boron.

Typical sources of aluminum oxide for the reaction mixture includealuminates, alumina, aluminum colloids, aluminum oxide coated on silicasol, hydrated alumina gels such as Al(OH)₃ and aluminum compounds suchas AlCl₃ and Al₂ (SO₄)₃. Typical sources of silicon oxide includesilicates, silica hydrogel, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicates, and silica hydroxides. Boron, aswell as gallium, germanium, titanium, indium, vanadium and iron, can beadded in forms corresponding to their aluminum and silicon counterparts.

A source zeolite reagent may provide a source of aluminum or boron. Inmost cases, the source zeolite also provides a source of silica. Thesource zeolite in its dealuminated or deboronated form may also be usedas a source of silica, with additional silicon added using, for example,the conventional sources listed above. Use of a source zeolite reagentas a source of alumina for the present process is more completelydescribed in U.S. Pat. No. 5,225,179, issued Jul. 6, 1993 to Nakagawaentitled "Method of Making Molecular Sieves", the disclosure of which isincorporated herein by reference.

Typically, an alkali metal hydroxide and/or an alkaline earth metalhydroxide, such as the hydroxide of sodium, potassium, lithium, cesium,rubidium, calcium, and magnesium, is used in the reaction mixture;however, this component can be omitted so long as the equivalentbasicity is maintained. The templating agent may be used to providehydroxide ion. Thus, it may be beneficial to ion exchange, for example,the halide for hydroxide ion, thereby reducing or eliminating the alkalimetal hydroxide quantity required. The alkali metal cation or alkalineearth cation may be part of the as-synthesized crystalline oxidematerial, in order to balance valence electron charges therein.

The reaction mixture is maintained at an elevated temperature until thecrystals of the SSZ-47 zeolite are formed. The hydrothermalcrystallization is usually conducted under autogenous pressure, at atemperature between 100° C. and 200° C., preferably between 135° C. and160° C. The crystallization period is typically greater than 1 day andpreferably from about 3 days to about 20 days.

Preferably, the zeolite is prepared using mild stirring or agitation.

During the hydrothermal crystallization step, the SSZ-47 crystals can beallowed to nucleate spontaneously from the reaction mixture. The use ofSSZ-47 crystals as seed material can be advantageous in decreasing thetime necessary for complete crystallization to occur. In addition,seeding can lead to an increased purity of the product obtained bypromoting the nucleation and/or formation of SSZ-47 over any undesiredphases. When used as seeds, SSZ-47 crystals are added in an amountbetween 0.1 and 10% of the weight of silica used in the reactionmixture.

Once the zeolite crystals have formed, the solid product is separatedfrom the reaction mixture by standard mechanical separation techniquessuch as filtration. The crystals are water-washed and then dried, e.g.,at 90° C. to 150° C. for from 8 to 24 hours, to obtain theas-synthesized SSZ-47 zeolite crystals. The drying step can be performedat atmospheric pressure or under vacuum.

SSZ-47 as prepared has a mole ratio of an oxide selected from siliconoxide, germanium oxide and mixtures thereof to an oxide selected fromaluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide,indium oxide, vanadium oxide and mixtures thereof greater than about 20;and has the X-ray diffraction lines of Table I below. SSZ-47 further hasa composition, as synthesized and in the anhydrous state, in terms ofmole ratios, shown in Table B below.

                  TABLE B                                                         ______________________________________                                        As-Synthesized SSZ-47                                                         ______________________________________                                        YO.sub.2 /W.sub.c O.sub.d                                                                   >30                                                             M.sub.2/n /YO.sub.2                                                                         0.01-0.03                                                       Q/YO.sub.2    0.02-0.05                                                       ______________________________________                                    

where Y, W, c, d, M and Q are as defined above.

SSZ-47 can be made essentially aluminum free, i.e., having a silica toalumina mole ratio of ∞. A method of increasing the mole ratio of silicato alumina is by using standard acid leaching or chelating treatments.However, essentially aluminum-free SSZ-47 can be synthesized directlyusing essentially aluminum-free silicon sources as the main tetrahedralmetal oxide component, if boron is also present. SSZ-47 can also beprepared directly as either an aluminosilicate or a borosilicate.

Lower silica to alumina ratios may also be obtained by using methodswhich insert aluminum into the crystalline framework. For example,aluminum insertion may occur by thermal treatment of the zeolite incombination with an alumina binder or dissolved source of alumina. Suchprocedures are described in U.S. Pat. No. 4,559,315, issued on Dec. 17,1985 to Chang et al.

It is believed that SSZ-47 is comprised of a new framework structure ortopology which is characterized by its X-ray diffraction pattern. SSZ-47zeolites, as-synthesized, have a crystalline structure whose X-raypowder diffraction pattern exhibit the characteristic lines shown inTable I and is thereby distinguished from other known zeolites.

                  TABLE I                                                         ______________________________________                                        As-Synthesized SSZ-47                                                         2 Theta.sup.(a)                                                                             d      Relative Intensity.sup.(b)                               ______________________________________                                        8.0           11.0   M                                                        9.6           9.19   W                                                        19.2          4.62   M                                                        20.65         4.30   VS                                                       22.35         3.97   S                                                        24.05         3.69   M                                                        26.1          3.41   W                                                        26.65         3.34   W                                                        27.35         3.26   S                                                        35.65         2.52   W                                                        ______________________________________                                         .sup.(a) ±0.2                                                              .sup.(b) The Xray patterns provided are based on a relative intensity         scale in which the strongest line in the Xray pattern is assigned a value     of 100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong     is between 40 and 60; VS(very strong) is greater than 60.                

After calcination, the SSZ-47 zeolites have a crystalline structurewhose X-ray powder diffraction pattern include the characteristic linesshown in Table II:

                  TABLE II                                                        ______________________________________                                        Calcined SSZ-47                                                               2 Theta.sup.(a)                                                                             d      Relative Intensity                                       ______________________________________                                        8.0           11.0   S                                                        9.6           9.19   W                                                        19.2          4.62   S                                                        20.65         4.30   VS                                                       22.35         3.97   S                                                        24.05         3.70   W-M                                                      26.1          3.41   W                                                        26.65         3.34   W-M                                                      27.35         3.26   S                                                        35.65         2.52   W                                                        ______________________________________                                         .sup.(a) ±0.2                                                         

The X-ray powder diffraction patterns were determined by standardtechniques. The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines,can be calculated.

The variation in the scattering angle (two theta) measurements, due toinstrument error and to differences between individual samples, isestimated at ±0.20 degrees.

The X-ray diffraction pattern of Table I is representative of"as-synthesized" or "as-made" SSZ-47 zeolites. Minor variations in thediffraction pattern can result from variations in the silica-to-aluminaor silica-to-boron mole ratio of the particular sample due to changes inlattice constants. In addition, sufficiently small crystals will affectthe shape and intensity of peaks, leading to significant peakbroadening.

Representative peaks from the X-ray diffraction pattern of calcinedSSZ-47 are shown in Table II. Calcination can also result in changes inthe intensities of the peaks as compared to patterns of the "as-made"material, as well as minor shifts in the diffraction pattern. Thezeolite produced by exchanging the metal or other cations present in thezeolite with various other cations (such as H⁺ or NH₄ ⁺) yieldsessentially the same diffraction pattern, although again, there may beminor shifts in the interplanar spacing and variations in the relativeintensities of the peaks. Notwithstanding these minor perturbations, thebasic crystal lattice remains unchanged by these treatments.

Crystalline SSZ-47 can be used as-synthesized, but preferably will bethermally treated (calcined). Usually, it is desirable to remove thealkali metal cation by ion exchange and replace it with hydrogen,ammonium, or any desired metal ion. The zeolite can be leached withchelating agents, e.g., EDTA or dilute acid solutions, to increase thesilica to alumina mole ratio. The zeolite can also be steamed; steaminghelps stabilize the crystalline lattice to attack from acids.

The zeolite can be used in intimate combination with hydrogenatingcomponents, such as tungsten, vanadium molybdenum, rhenium, nickelcobalt, chromium, manganese, or a noble metal, such as palladium orplatinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the zeolite by replacing some of thecations in the zeolite with metal cations via standard ion exchangetechniques (see, for example, U.S. Pat. Nos. 3,140,249 issued Jul. 7,1964 to Plank et al.; 3,140,251 issued Jul. 7, 1964 to Plank et al.; and3,140,253 issued Jul. 7, 1964 to Plank et al.). Typical replacingcations can include metal cations, e.g., rare earth, Group IA, Group IIAand Group VIII metals, as well as their mixtures. Of the replacingmetallic cations, cations of metals such as rare earth, Mn, Ca, Mg, Zn,Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are particularly preferred.

The hydrogen, ammonium, and metal components can be ion-exchanged intothe SSZ-47. The zeolite can also be impregnated with the metals, or, themetals can be physically and intimately admixed with the zeolite usingstandard methods known to the art.

Typical ion-exchange techniques involve contacting the synthetic zeolitewith a solution containing a salt of the desired replacing cation orcations. Although a wide variety of salts can be employed, chlorides andother halides, acetates, nitrates, and sulfates are particularlypreferred. The zeolite is usually calcined prior to the ion-exchangeprocedure to remove the organic matter present in the channels and onthe surface, since this results in a more effective ion exchange.Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. No. 3,140,249 issued on Jul. 7, 1964 toPlank et al.; U.S. Pat. No. 3,140,251 issued on Jul. 7, 1964 to Plank etal.; and U.S. Pat. No. 3,140,253 issued on Jul. 7, 1964 to Plank et al.

Following contact with the salt solution of the desired replacingcation, the zeolite is typically washed with water and dried attemperatures ranging from 65° C. to about 200° C. After washing, thezeolite can be calcined in air or inert gas at temperatures ranging fromabout 200° C. to about 800° C. for periods of time ranging from 1 to 48hours, or more, to produce a catalytically active product especiallyuseful in hydrocarbon conversion processes.

Regardless of the cations present in the synthesized form of SSZ-47, thespatial arrangement of the atoms which form the basic crystal lattice ofthe zeolite remains essentially unchanged.

SSZ-47 can be formed into a wide variety of physical shapes. Generallyspeaking, the zeolite can be in the form of a powder, a granule, or amolded product, such as extrudate having a particle size sufficient topass through a 2-mesh (Tyler) screen and be retained on a 400-mesh(Tyler) screen. In cases where the catalyst is molded, such as byextrusion with an organic binder, the aluminosilicate can be extrudedbefore drying, or, dried or partially dried and then extruded.

SSZ-47 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

Hydrocarbon Conversion Processes

SSZ-47 zeolites are useful in hydrocarbon conversion reactions.Hydrocarbon conversion reactions are chemical and catalytic processes inwhich carbon containing compounds are changed to different carboncontaining compounds. Examples of hydrocarbon conversion reactions inwhich SSZ-47 are expected to be useful include hydrocracking, dewaxing,catalytic cracking and olefin and aromatics formation reactions. Thecatalysts are also expected to be useful in other petroleum refining andhydrocarbon conversion reactions such as isomerizing n-paraffins andnaphthenes, polymerizing and oligomerizing olefinic or acetyleniccompounds such as isobutylene and butene-1, reforming, isomerizingpolyalkyl substituted aromatics (e.g., m-xylene), and disproportionatingaromatics (e.g., toluene) to provide mixtures of benzene, xylenes andhigher methylbenzenes and oxidation reactions. Also included arerearrangement reactions to make various naphthalene derivatives. TheSSZ-47 catalysts may have high selectivity, and under hydrocarbonconversion conditions can provide a high percentage of desired productsrelative to total products.

SSZ-47 zeolites can be used in processing hydrocarbonaceous feedstocks.Hydrocarbonaceous feedstocks contain carbon compounds and can be frommany different sources, such as virgin petroleum fractions, recyclepetroleum fractions, shale oil, liquefied coal, tar sand oil, syntheticparaffins from NAO, recycled plastic feedstocks and, in general, can beany carbon containing feedstock susceptible to zeolitic catalyticreactions. Depending on the type of processing the hydrocarbonaceousfeed is to undergo, the feed can contain metal or be free of metals, itcan also have high or low nitrogen or sulfur impurities. It can beappreciated, however, that in general processing will be more efficient(and the catalyst more active) the lower the metal, nitrogen, and sulfurcontent of the feedstock.

The conversion of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the conversion process andmethod of operation.

Other reactions which can be performed using the catalyst of thisinvention containing a metal, e.g., a Group VIII metal such platinum,include hydrogenation-dehydrogenation reactions, denitrogenation anddesulfurization reactions.

The following table indicates typical reaction conditions which may beemployed when using catalysts comprising SSZ-47 in the hydrocarbonconversion reactions of this invention. Preferred conditions areindicated in parentheses.

    ______________________________________                                        Process   Temp., ° C.                                                                        Pressure   LHSV                                         ______________________________________                                        Hydrocracking                                                                           175-485     0.5-350 bar                                                                              0.1-30                                       Dewaxing  200-475     15-3000 psig                                                                             0.1-20                                                 (250-450)   (200-3000) (0.2-10)                                     Aromatics 400-600     atm.-10 bar                                                                              0.1-15                                       formation (480-550)                                                           Cat. cracking                                                                           127-885     subatm.-.sup.1                                                                           0.5-50                                                             (atm.-5 atm.)                                           Oligomerization                                                                         .sup. 232-649.sup.2                                                                       0.1-50 atm..sup.2,3                                                                      .sup. 0.2-50.sup.2                                     .sup.  10-232.sup.4                                                                       --         0.05-20.sup.5                                          .sup.  (27-204).sup.4                                                                     --         .sup. (0.1-10).sup.5                         Paraffins to                                                                            100-700       0-1000 psig                                                                            .sup. 0.5-40.sup.5                           aromatics                                                                     Condensation of                                                                         260-538     0.5-1000 psig                                                                            .sup. 0.5-50.sup.5                           alcohols                                                                      Isomerization                                                                            93-538      50-1000 psig                                                                              1-10                                                 (204-315)               (1-4)                                       Xylene    .sup. 260-593.sup.2                                                                       0.5-50 atm..sup.2                                                                        .sup.  0.1-100.sup.5                         isomerization                                                                           .sup. (315-566).sup.2                                                                     (1-5 atm).sup.2                                                                          .sup. (0.5-50).sup.5                                   .sup.  38-371.sup.4                                                                       1-200 atm..sup.4                                                                         0.5-50                                       ______________________________________                                         .sup.1 Several hundred atmospheres                                            .sup.2 Gas phase reaction                                                     .sup.3 Hydrocarbon partial pressure                                           .sup.4 Liquid phase reaction                                                  .sup.5 WHSV                                                              

Other reaction conditions and parameters are provided below.

Hydrocracking

Using a catalyst which comprises SSZ-47, preferably predominantly in thehydrogen form, and a hydrogenation promoter, heavy petroleum residualfeedstocks, cyclic stocks and other hydrocrackate charge stocks can behydrocracked using the process conditions and catalyst componentsdisclosed in the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat.No. 5,316,753.

The hydrocracking catalysts contain an effective amount of at least onehydrogenation component of the type commonly employed in hydrocrackingcatalysts. The hydrogenation component is generally selected from thegroup of hydrogenation catalysts consisting of one or more metals ofGroup VIB and Group VIII, including the salts, complexes and solutionscontaining such. The hydrogenation catalyst is preferably selected fromthe group of metals, salts and complexes thereof of the group consistingof at least one of platinum, palladium, rhodium, iridium, ruthenium andmixtures thereof or the group consisting of at least one of nickel,molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.Reference to the catalytically active metal or metals is intended toencompass such metal or metals in the elemental state or in some formsuch as an oxide, sulfide, halide, carboxylate and the like. Thehydrogenation catalyst is present in an effective amount to provide thehydrogenation function of the hydrocracking catalyst, and preferably inthe range of from 0.05 to 25% by weight.

Dewaxing

SSZ-47, preferably predominantly in the hydrogen form, can be used todewax hydrocarbonaceous feeds by selectively removing straight chainparaffins. Typically, the viscosity index of the dewaxed product isimproved (compared to the waxy feed) when the waxy feed is contactedwith SSZ-47 under isomerization dewaxing conditions.

The catalytic dewaxing conditions are dependent in large measure on thefeed used and upon the desired pour point. Hydrogen is preferablypresent in the reaction zone during the catalytic dewaxing process. Thehydrogen to feed ratio is typically between about 500 and about 30,000SCF/bbl (standard cubic feet per barrel), preferably about 1000 to about20,000 SCF/bbl. Generally, hydrogen will be separated from the productand recycled to the reaction zone. Typical feedstocks include light gasoil, heavy gas oils and reduced crudes boiling above about 350° F.

A typical dewaxing process is the catalytic dewaxing of a hydrocarbonoil feedstock boiling above about 350° F. and containing straight chainand slightly branched chain hydrocarbons by contacting the hydrocarbonoil feedstock in the presence of added hydrogen gas at a hydrogenpressure of about 15-3000 psi with a catalyst comprising SSZ-47 and atleast one Group VIII metal.

The SSZ-47 hydrodewaxing catalyst may optionally contain a hydrogenationcomponent of the type commonly employed in dewaxing catalysts. See theaforementioned U.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 forexamples of these hydrogenation components.

The hydrogenation component is present in an effective amount to providean effective hydrodewaxing and hydroisomerization catalyst preferably inthe range of from about 0.05 to 5% by weight. The catalyst may be run insuch a mode to increase isodewaxing at the expense of crackingreactions.

The feed may be hydrocracked, followed by dewaxing. This type of twostage process and typical hydrocracking conditions are described in U.S.Pat. No. 4,921,594, issued May 1, 1990 to Miller, which is incorporatedherein by reference in its entirety.

SSZ-47 may also be utilized as a dewaxing catalyst in the form of alayered catalyst. That is, the catalyst comprises a first layercomprising zeolite SSZ-47 and at least one Group VIII metal, and asecond layer comprising an aluminosilicate zeolite which is more shapeselective than zeolite SSZ-47. The use of layered catalysts is disclosedin U.S. Pat. No. 5,149,421, issued Sep. 22, 1992 to Miller, which isincorporated by reference herein in its entirety. The layering may alsoinclude a bed of SSZ-47 layered with a non-zeolitic component designedfor either hydrocracking or hydrofinishing.

SSZ-47 may also be used to dewax raffinates, including bright stock,under conditions such as those disclosed in U. S. Pat. No. 4,181,598,issued Jan. 1, 1980 to Gillespie et al., which is incorporated byreference herein in its entirety.

It is often desirable to use mild hydrogenation (sometimes referred toas hydrofinishing) to produce more stable dewaxed products. Thehydrofinishing step can be performed either before or after the dewaxingstep, and preferably after. Hydrofinishing is typically conducted attemperatures ranging from about 190° C. to about 340° C. at pressuresfrom about 400 psig to about 3000 psig at space velocities (LHSV)between about 0.1 and 20 and a hydrogen recycle rate of about 400 to1500 SCF/bbl. The hydrogenation catalyst employed must be active enoughnot only to hydrogenate the olefins, diolefins and color bodies whichmay be present, but also to reduce the aromatic content. Suitablehydrogenation catalyst are disclosed in U. S. Pat. No. 4,921,594, issuedMay 1, 1990 to Miller, which is incorporated by reference herein in itsentirety. The hydrofinishing step is beneficial in preparing anacceptably stable product (e.g., a lubricating oil) since dewaxedproducts prepared from hydrocracked stocks tend to be unstable to airand light and tend to form sludges spontaneously and quickly.

Lube oil may be prepared using SSZ-47. For example, a C₂₀₊ lube oil maybe made by isomerizing a C₂₀, olefin feed over a catalyst comprisingSSZ-47 in the hydrogen form and at least one Group VIII metal.Alternatively, the lubricating oil may be made by hydrocracking in ahydrocracking zone a hydrocarbonaceous feedstock to obtain an effluentcomprising a hydrocracked oil, and catalytically dewaxing the effluentat a temperature of at least about 400° F. and at a pressure of fromabout 15 psig to about 3000 psig in the presence of added hydrogen gaswith a catalyst comprising SSZ-47 in the hydrogen form and at least oneGroup VIII metal.

Aromatics Formation

SSZ-47 can be used to convert light straight run naphthas and similarmixtures to highly aromatic mixtures. Thus, normal and slightly branchedchained hydrocarbons, preferably having a boiling range above about 40°C. and less than about 200° C., can be converted to products having asubstantial higher octane aromatics content by contacting thehydrocarbon feed with a catalyst comprising SSZ-47. It is also possibleto convert heavier feeds into BTX or naphthalene derivatives of valueusing a catalyst comprising SSZ-47.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium or tin or amixture thereof may also be used in conjunction with the Group VIIImetal compound and preferably a noble metal compound. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inreforming catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

It is critical to the selective production of aromatics in usefulquantities that the conversion catalyst be substantially free ofacidity, for example, by neutralizing the zeolite with a basic metal,e.g., alkali metal, compound. Methods for rendering the catalyst free ofacidity are known in the art. See the aforementioned U.S. Pat. No.4,910,006 and U.S. Pat. No. 5,316,753 for a description of such methods.

The preferred alkali metals are sodium, potassium, rubidium and cesium.The zeolite itself can be substantially free of acidity only at veryhigh silica:alumina mole ratios.

Catalytic Cracking

Hydrocarbon cracking stocks can be catalytically cracked in the absenceof hydrogen using SSZ-47, preferably predominantly in the hydrogen form.

When SSZ-47 is used as a catalytic cracking catalyst in the absence ofhydrogen, the catalyst may be employed in conjunction with traditionalcracking catalysts, e.g., any aluminosilicate heretofore employed as acomponent in cracking catalysts. Typically, these are large pore,crystalline aluminosilicates. Examples of these traditional crackingcatalysts are disclosed in the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No 5,316,753. When a traditional cracking catalyst (TC)component is employed, the relative weight ratio of the TC to the SSZ-47is generally between about 1:10 and about 500:1, desirably between about1:10 and about 200:1, preferably between about 1:2 and about 50:1, andmost preferably is between about 1:1 and about 20:1. The novel zeoliteand/or the traditional cracking component may be further ion exchangedwith rare earth ions to modify selectivity.

The cracking catalysts are typically employed with an inorganic oxidematrix component. See the aforementioned U.S. Pat. No. 4,910,006 andU.S. Pat. No. 5,316,753 for examples of such matrix components.

Isomerization

The present catalyst is highly active and highly selective forisomerizing C₄ to C₇ hydrocarbons. The activity means that the catalystcan operate at relatively low temperature which thermodynamically favorshighly branched paraffins. Consequently, the catalyst can produce a highoctane product. The high selectivity means that a relatively high liquidyield can be achieved when the catalyst is run at a high octane.

The present process comprises contacting the isomerization catalyst,i.e., a catalyst comprising SSZ-47 in the hydrogen form, with ahydrocarbon feed under isomerization conditions. The feed is preferablya light straight run fraction, boiling within the range of 30° F. to250° F. and preferably from 60° F. to 200° F. Preferably, thehydrocarbon feed for the process comprises a substantial amount of C₄ toC₇ normal and slightly branched low octane hydrocarbons, more preferablyC₅ and C₆ hydrocarbons.

It is preferable to carry out the isomerization reaction in the presenceof hydrogen. Preferably, hydrogen is added to give a hydrogen tohydrocarbon ratio (H₂ /HC) of between 0.5 and 10 H₂ /HC, more preferablybetween 1 and 8 H₂ /HC. See the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753 for a further discussion of isomerizationprocess conditions.

A low sulfur feed is especially preferred in the present process. Thefeed preferably contains less than 10 ppm, more preferably less than 1ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feedwhich is not already low in sulfur, acceptable levels can be reached byhydrogenating the feed in a presaturation zone with a hydrogenatingcatalyst which is resistant to sulfur poisoning. See the aforementionedU.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 for a furtherdiscussion of this hydrodesulfurization process.

It is preferable to limit the nitrogen level and the water content ofthe feed. Catalysts and processes which are suitable for these purposesare known to those skilled in the art.

After a period of operation, the catalyst can become deactivated bysulfur or coke. See the aforementioned U.S. Pat. No. 4,910,006 and U.S.Pat. No. 5,316,753 for a further discussion of methods of removing thissulfur and coke, and of regenerating the catalyst.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium and tin mayalso be used in conjunction with the noble metal. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inisomerizing catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

Alkylation and Transalkylation

SSZ-47 can be used in a process for the alkylation or transalkylation ofan aromatic hydrocarbon. The process comprises contacting the aromatichydrocarbon with a C₂ to C₆ olefin alkylating agent or a polyalkylaromatic hydrocarbon transalkylating agent, under at least partialliquid phase conditions, and in the presence of a catalyst comprisingSSZ-47.

SSZ-47 can also be used for removing benzene from gasoline by alkylatingthe benzene as described above and removing the alkylated product fromthe gasoline.

For high catalytic activity, the SSZ-47 zeolite should be predominantlyin its hydrogen ion form. It is preferred that, after calcination, atleast 80% of the cation sites are occupied by hydrogen ions and/or rareearth ions.

Examples of suitable aromatic hydrocarbon feedstocks which may bealkylated or transalkylated by the process of the invention includearomatic compounds such as benzene, toluene and xylene. The preferredaromatic hydrocarbon is benzene. There may be occasions wherenaphthalene derivatives may be desirable. Mixtures of aromatichydrocarbons may also be employed.

Suitable olefins for the alkylation of the aromatic hydrocarbon arethose containing 2 to 20, preferably 2 to 4, carbon atoms, such asethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, ormixtures thereof. There may be instances where pentenes are desirable.The preferred olefins are ethylene and propylene. Longer chain alphaolefins may be used as well.

When transalkylation is desired, the transalkylating agent is apolyalkyl aromatic hydrocarbon containing two or more alkyl groups thateach may have from 2 to about 4 carbon atoms. For example, suitablepolyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkylaromatic hydrocarbons, such as diethylbenzene, triethylbenzene,diethylmethylbenzene (diethyltoluene), di-isopropylbenzene,di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkylaromatic hydrocarbons are the dialkyl benzenes. A particularly preferredpolyalkyl aromatic hydrocarbon is di-isopropylbenzene.

When alkylation is the process conducted, reaction conditions are asfollows. The aromatic hydrocarbon feed should be present instoichiometric excess. It is preferred that molar ratio of aromatics toolefins be greater than four-to-one to prevent rapid catalyst fouling.The reaction temperature may range from 100° F. to 600° F., preferably250° F. to 450° F. The reaction pressure should be sufficient tomaintain at least a partial liquid phase in order to retard catalystfouling. This is typically 50 psig to 1000 psig depending on thefeedstock and reaction temperature. Contact time may range from 10seconds to 10 hours, but is usually from 5 minutes to an hour. Theweight hourly space velocity (WHSV), in terms of grams (pounds) ofaromatic hydrocarbon and olefin per gram (pound) of catalyst per hour,is generally within the range of about 0.5 to 50.

When transalkylation is the process conducted, the molar ratio ofaromatic hydrocarbon will generally range from about 1:1 to 25:1, andpreferably from about 2:1 to 20:1. The reaction temperature may rangefrom about 1 00° F. to 600° F., but it is preferably about 250° F. to450° F. The reaction pressure should be sufficient to maintain at leasta partial liquid phase, typically in the range of about 50 psig to 1000psig, preferably 300 psig to 600 psig. The weight hourly space velocitywill range from about 0.1 to 10. U.S. Pat. No. 5,082,990 issued on Jan.21, 1992 to Hsieh, et al. describes such processes and is incorporatedherein by reference.

Conversion of Paraffins to Aromatics

SSZ-47 can be used to convert light gas C₂ -C₆ paraffins to highermolecular weight hydrocarbons including aromatic compounds. Preferably,the zeolite will contain a catalyst metal or metal oxide wherein saidmetal is selected from the group consisting of Groups IB, IIB, VIII andIIIA of the Periodic Table. Preferably, the metal is gallium, niobium,indium or zinc in the range of from about 0.05 to 5% by weight.

Xylene Isomerization

SSZ-47 may also be useful in a process for isomerizing one or morexylene isomers in a C₈ aromatic feed to obtain ortho-, meta-, andpara-xylene in a ratio approaching the equilibrium value. In particular,xylene isomerization is used in conjunction with a separate process tomanufacture para-xylene. For example, a portion of the para-xylene in amixed C₈ aromatics stream may be recovered by crystallization andcentrifugation. The mother liquor from the crystallizer is then reactedunder xylene isomerization conditions to restore ortho-, meta- andpara-xylenes to a near equilibrium ratio. At the same time, part of theethylbenzene in the mother liquor is converted to xylenes or to productswhich are easily separated by filtration. The isomerate is blended withfresh feed and the combined stream is distilled to remove heavy andlight by-products. The resultant C₈ aromatics stream is then sent to thecrystallizer to repeat the cycle.

Optionally, isomerization in the vapor phase is conducted in thepresence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene(e.g., ethylbenzene). If hydrogen is used, the catalyst should compriseabout 0.1 to 2.0 wt % of a hydrogenation/dehydrogenation componentselected from Group VIII (of the Periodic Table) metal component,especially platinum or nickel. By Group VIII metal component is meantthe metals and their compounds such as oxides and sulfides.

Optionally, the isomerization feed may contain 10 to 90 wt % of adiluent such as toluene, trimethylbenzene, naphthenes or paraffins.

Oligomerization

It is expected that SSZ-47 can also be used to oligomerize straight andbranched chain olefins having from about 2 to 21 and preferably 2-5carbon atoms. The oligomers which are the products of the process aremedium to heavy olefins which are useful for both fuels, i.e., gasolineor a gasoline blending stock and chemicals.

The oligomerization process comprises contacting the olefin feedstock inthe gaseous or liquid phase with a catalyst comprising SSZ-47.

The zeolite can have the original cations associated therewith replacedby a wide variety of other cations according to techniques well known inthe art. Typical cations would include hydrogen, ammonium and metalcations including mixtures of the same. Of the replacing metalliccations, particular preference is given to cations of metals such asrare earth metals, manganese, calcium, as well as metals of Group II ofthe Periodic Table, e.g., zinc, and Group VIII of the Periodic Table,e.g., nickel. One of the prime requisites is that the zeolite have afairly low aromatization activity, i.e., in which the amount ofaromatics produced is not more than about 20% by weight. This isaccomplished by using a zeolite with controlled acid activity [alphavalue] of from about 0.1 to about 120, preferably from about 0.1 toabout 100, as measured by its ability to crack n-hexane.

Alpha values are defined by a standard test known in the art, e.g., asshown in U.S. Pat. No. 3,960,978 issued on Jun. 1, 1976 to Givens et al.which is incorporated totally herein by reference. If required, suchzeolites may be obtained by steaming, by use in a conversion process orby any other method which may occur to one skilled in this art.

Condensation of Alcohols

SSZ-47 can be used to condense lower aliphatic alcohols having 1 to 10carbon atoms to a gasoline boiling point hydrocarbon product comprisingmixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S.Pat. No. 3,894,107, issued Jul. 8, 1975 to Butter et al., describes theprocess conditions used in this process, which patent is incorporatedtotally herein by reference.

The catalyst may be in the hydrogen form or may be base exchanged orimpregnated to contain ammonium or a metal cation complement, preferablyin the range of from about 0.05 to 5% by weight. The metal cations thatmay be present include any of the metals of the Groups I through VIII ofthe Periodic Table. However, in the case of Group IA metals, the cationcontent should in no case be so large as to effectively inactivate thecatalyst, nor should the exchange be such as to eliminate all acidity.There may be other processes involving treatment of oxygenatedsubstrates where a basic catalyst is desired.

Other Uses for SSZ-47

SSZ-47 can also be used as an adsorbent with high selectivities based onmolecular sieve behavior and also based upon preferential hydrocarbonpacking within the pores.

SSZ-47 may also be used for the catalytic reduction of the oxides ofnitrogen in a gas stream. Typically, the gas stream also containsoxygen, often a stoichiometric excess thereof. Also, the SSZ-47 maycontain a metal or metal ions within or on it which are capable ofcatalyzing the reduction of the nitrogen oxides. Examples of such metalsor metal ions include copper, cobalt and mixtures thereof.

One example of such a process for the catalytic reduction of oxides ofnitrogen in the presence of a zeolite is disclosed in U.S. Pat. No.4,297,328, issued Oct. 27, 1981 to Ritscher et al., which isincorporated by reference herein. There, the catalytic process is thecombustion of carbon monoxide and hydrocarbons and the catalyticreduction of the oxides of nitrogen contained in a gas stream, such asthe exhaust gas from an internal combustion engine. The zeolite used ismetal ion-exchanged, doped or loaded sufficiently so as to provide aneffective amount of catalytic copper metal or copper ions within or onthe zeolite. In addition, the process is conducted in an excess ofoxidant, e.g., oxygen.

EXAMPLES

The following examples demonstrate but do not limit the presentinvention. The templating agents indicated in Table C below are used inthese examples.

                  TABLE C                                                         ______________________________________                                         ##STR1##                                                                     3-(Trimethylammonium)-bicyclo[3.2.1]octane cation                             (Template A)                                                                   ##STR2##                                                                     3,3-Dimethyl-3-ozoniabicyclo[4.2.1]nonane cation                              (Template B)                                                                  ______________________________________                                    

The anion (X⁻) associated with the cation may be any anion which is notdetrimental to the formation of the zeolite. Representative anionsinclude halogen, e.g., fluoride, chloride, bromide and iodide,hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and thelike. Hydroxide is the most preferred anion.

Example 1 Synthesis of N,N,N-Trimethylammonium-3-bicyclo[3.2.1] octanecation (Template A)

A 5 liter three-necked round bottom flask is equipped with a mechanicalstirrer, liquid addition funnel that has a pressure equalization arm,and a N₂ inlet valve. The reaction is vented to an oil bubbler. Theflask is charged with 1260 ml. of anhydrous ether. 50.5 Grams ofpowdered lithium aluminum hydride ("LAH") are carefully added to thestirring ether solution. The liquid addition funnel is charged with148.8 g. of 3,4-dichlorobicyclo[3.2.1]-oct-2-ene (80% exo and 20% endo)and 630 ml. of anhydrous methylene chloride. The reaction vessel isplaced in an acetone bath. The 3,4-dichlorobicyclo[3.2.1]oct-2-enesolution is added dropwise to the LAH suspension over a ten minuteperiod. Dry ice is added as necessary to the acetone bath to control theslight exotherm. The cooling bath is removed and replaced with a heatingmantle. A gentle reflux is maintained for 24 hours. The excess LAH isdecomposed by first slowly adding 50.5 g. of water to the reactionmixture. Next, 50.5 g. of an aqueous 15% NaOH solution is added.Finally, 151.5 g. of water is added to the reaction mixture. The lithiumand aluminum salts are removed by filtration and washed with methylenechloride. The filtrate is dried over anhydrous magnesium sulfate. Thefiltrate is then filtered and the ether and methylene chloride arestripped off on a rotovap at 50° (maximum vacuum 60 mm. Hg). The productis then distilled through a 30 cm. Vigreux column to give 80.4 g. of3-chloro-[3.2.1]oct-2-ene as a colorless oil, b.p. 73-80° (20 mm. Hg).

A 2 liter round bottom flask is equipped with a magnetic stir bar. Theflask is charged with 907.1 ml. of sulfuric acid. Stirring is begun asthe flask is cooled in an ice bath. 80.2 g. of3-chlorobicyclo[3.2.1]oct-2-ene are added in one portion. The mixture isstirred and allowed to warm to room temperature over a 4 hour period andis then stirred overnight. The resulting solution is poured onto 3 kg.of ice. After the ice has melted, the mixture is extracted with three500 ml. portions of ether. The combined ether extracts are washed onetime with 400 ml. of water and the dried over anhydrous magnesiumsulfate. The ether is removed by carefully distillation, and the crudeproduct is sublimed at a bath temperature of 85°(5 mm. Hg). The crudeproduct is sublimed twice to give 53.4 g. of bicyclo[3.2.1]octan-3-one.

A 2 liter Parr reactor is charge with 53.3 g. ofbicyclo[3.2.1]octan-3-one, 59.6 g. of DMF and 37 g. of 96% formic acid.The reactor is sealed and placed in a 190° oven for 30 hours. Thereactor is allowed to cool to room temperature before being vented. Thecontents are transfer to a separatory funnel. 250 ml. of water are addedto the funnel and the pH is adjusted to <2 with concentrated HCI. Theaqueous layer is washed with three 250 ml. portions of methylenechloride. The pH of the aqueous phase is then adjusted to >12 with a 50%NaOH solution. The aqueous phase is extracted with three 250 ml.portions of methylene chloride. The combine extracts are dried overanhydrous sodium sulfate. Filtration and removal of the methylenechloride yield 61.3 g. of dimethylamino-3-bicyclo[3.2.1]octane.

A 500 ml. round bottom flask is equipped with a magnetic stir bar and aliquid addition funnel that has an equalization arm. The flask ischarged with 61.2 g. of dimethylamino-3-bicyclo[3.2.1]octane and 200 ml.of methanol. The addition funnel is charge with 114.6 g. of iodomethane.The iodomethane is added dropwise to the reaction mixture over a 15minute period. No exotherm is detected. The reaction is stirred at roomtemperature for 14 days. Ether is added to the reaction mixture and theproduct is collected by filtration. Recrystallization from hotacetone/IPA yields 86.3 g. of the desired quaternary ammonium salt.

The product is converted to the hydroxide salt by treatment with Bio-RadAG1-X8 anion exchange resin. The hydroxide ion concentration isdetermined by titration of the resulting solution using phenolphthaleinas the indicator.

Example 2 Synthesis of N.N-Dimethyl-3 -azoniabicyclo[4.2.1]nonane cation(Template B)

A 5 liter three-necked round bottom flask is equipped with a mechanicalstirrer, liquid addition funnel that has a pressure equalization arm,and a N₂ inlet valve. The reaction is vented to an oil bubbler. Theflask is charged with 1700 ml. of anhydrous ether. 67.9 g. of powderedLAH are carefully added to the stirring ether solution. The liquidaddition funnel is charged with 200.0 g. of3,4-dichlorobicyclo[3.2.1]-oct-2-ene (80% exo and 20% endo) and 850 ml.of anhydrous methylene chloride. The reaction vessel is placed in anacetone bath. The 3,4-dichlorobicyclo[3.2.1]oct-2-ene solution is addeddropwise to the LAH suspension over a twenty minute period. Dry ice isadded as necessary to the acetone bath to control the slight exotherm.The cooling bath is removed and replaced with a heating mantle. A gentlereflux is maintained for 24 hours. The excess LAH is decomposed by firstslowly adding 67.9 g. of water to the reaction mixture. Next, 67.9 g. ofan aqueous 15% NaOH solution is added. Finally, 203.7 g. of water areadded to the reaction mixture. The lithium and aluminum salts areremoved by filtration and washed with methylene chloride. The filtrateis dried over anhydrous magnesium sulfate. The filtrate is then filteredand the ether and methylene chloride are stripped off on a rotovap at50° (maximum vacuum 60 mm. Hg). The product is then distilled through a30 cm. Vigreux column to give 100.0 g. of 3-chloro-[3.2.1]oct-2-ene as acolorless oil, b.p. 71-78 (20 mm. Hg).

A 2 liter round bottom flask is equipped with a magnetic stir bar. Theflask is charged with 1132.2 ml. of sulfuric acid. Stirring is begun asthe flask is cooled in an ice bath. 99.8 g. of3-chlorobicyclo[3.2.1]oct-2-ene are added in one portion. The mixture isstirred and allowed to warm to room temperature over a 4 hour period andis then stirred overnight. The resulting solution is poured onto 3 kg.of ice. After the ice has melted, the mixture is extracted with three500 ml. portions of ether. The combined ether extracts are washed withthree 250 ml. portions of water and the dried over anhydrous magnesiumsulfate. The ether is removed by careful distillation, and the crudeproduct is sublimed at a bath temperature of 85° (5 mm. Hg). The crudeproduct is sublimed thrice to give 43.3 g. of bicyclo[3.2.1]octan-3-one.

A 1 liter round bottom flask is equipped with a magnetic stir bar and aliquid addition funnel that has an equalization arm. The flask ischarged with 43.2 g. of bicyclo[3.2.1]octan-3-one and 345 ml. of 96%formic acid. The liquid addition funnel is charged with 60.8 g. ofhydroxylamine-O-sulfonic acid and 175 ml. of 96% formic acid. Thehydroxylamine-O-sulfonic acid solution is added dropwise to the reactionmixture over a 15 minute period. A slight exotherm was noted. The liquidaddition funnel is replaced with a reflux condenser and the reaction isheated to reflux and stirred overnight. The reaction mixture is pouredonto 2 kg. of ice. The pH is adjusted to >12 by carefully adding 50%NaOH. The mixture is transferred to a separatory funnel and extractedwith four 250 ml. portions of methylene chloride. The combined organicextracts are dried over anhydrous sodium sulfate. Filtration and removalof the methylene chloride yields 38.8 g of crude product. Chromatographyon 800 g. of 230-400 mesh silica gel (eluent: 2% methanol/ 98%chloroform) yields 32.4 g. of 3-azabicyclo[4.2.1]nonan-4-one.

A 1 liter three-necked round bottom flask is equipped with a mechanicalstirrer, liquid addition funnel that has a pressure equalization arm,and a N₂ inlet valve. The reaction is vented to an oil bubbler. Theflask is charged with 350 ml. of anhydrous ether. 13.9 g. of powderedLAH are carefully added to the stirring ether solution. The liquidaddition funnel is charged with 32.4 g. of3-azabicyclo[4.2.1]nonan-4-one and 175 ml. of anhydrous methylenechloride. The reaction vessel is placed in an acetone bath. The3-azabicyclo[4.2.1]nonan-4-one solution is added dropwise to the LAHsuspension over a twenty minute period. Dry ice is added as necessary tothe acetone bath to control the slight exotherm. The cooling bath isremoved and the reaction is allowed to warm to room temperature forthree days. The excess LAH is decomposed by first slowly adding 13.9 g.of water to the reaction mixture. Next, 13.9 g. of an aqueous 15% NaOHsolution is added. Finally, 41.7 g. of water are added to the reactionmixture. The lithium and aluminum salts are removed by filtration andwashed with methylene chloride. The filtrate is dried over anhydroussodium sulfate. Filtration and removal of the ether and methylenechloride yields 22.8 g. of 3-azabicyclo[4.2.1]nonane.

A 250 ml. round bottom flask is equipped with a magnetic stir bar and aliquid addition funnel that has an equalization arm. The flask ischarged with 5.0 g. of 3-azabicyclo[4.2.1]nonane, 6.0 g. of potassiumbicarbonate and 40.0 ml. of methanol. The addition funnel is charge with17.2 g. of iodomethane. The iodomethane is added dropwise to thereaction mixture over a 10 minute period. No exotherm is detected. Thereaction is stirred at room temperature for 7 days. The methanol isremoved from the reaction mixture on the rotovap. 100 ml. of chloroformare added to the solid residue. After stirring for 5 minutes, the solidsare removed by filtration. The chloroform is removed from the filtrateand the solid residue is recrystallized from hot IPA/methanol yielding8.9 g. of the desired quaternary ammonium salt.

The product is converted to the hydroxide salt by treatment with Bio-RadAGI-X8 anion exchange resin. The hydroxide ion concentration isdetermined by titration of the resulting solution using phenolphthaleinas the indicator.

Example 3 Preparation of Aluminosilicate SSZ-47 Starting SiO₂ Al₂ O₃ =35

0.06 Gram of a solution of Template A (0.50 mmol OH⁻ /g) is mixed with8.43 grams of water, 0.22 gram of isobutylamine and 3.0 grams of 1.0 NKOH. Reheis F2000 (0.088 gram) is added to this solution and, followingcomplete dissolution of the solid, 0.90 gram of Cabosil M-5 silica isadded. This mixture is heated at 170° C. and rotated at 43 rpm for 14days, after which a settled product is obtained. Analysis by XRD showsthe product to be SSZ-47. The XRD data appears in Table III below.

                  TABLE III                                                       ______________________________________                                        2 Theta         d      I/I.sub.0 × 100                                  ______________________________________                                        8.0             11.0   22                                                     9.6             9.19   4                                                      13.0            6.81   4                                                      15.2            5.81   3                                                      16.0            5.53   6                                                      19.2            4.62   35                                                     19.9            4.46   3                                                      20.65           4.30   100                                                    22.3            3.98   53                                                     24.05           3.69   22                                                     24.7(Sh)        3.60   3                                                      26.1            3.41   10                                                     26.65           3.34   16                                                     27.3            3.26   41                                                     27.5(Sh)        3.24   18                                                     28.2            3.16   3                                                      28.95           3.08   3                                                      33.25           2.69   8                                                      34.95           2.57   3                                                      35.55           2.52   6                                                      36.5            2.46   2                                                      37.55           2.39   2                                                      38.85           2.32   2                                                      39.25           2.29   2                                                      ______________________________________                                    

Example 4 Seeded Preparation of Aluminosilicate SSZ-47

The reaction described in Example 3 is repeated, with the exception ofseeding with 0.004 gram of SSZ-47 crystals. In this case, SSZ-47 isobtained in 9 days. The product has a silica/alumina mole ratio of 32.

Example 5 Preparation of Aluminosilicate SSZ-47 Starting SiO₂ /Al₂ O₃=35

The reaction described in Example 3 is repeated, with the exception that3.0 grams of 1N NaOH is used. After 6 days at 170° C. and 43 rpm aproduct is isolated and determined by XRD to be SSZ-47.

Example 6 Preparation of Borosilicate SSZ-47 Starting SiO₂ /B₂ O₃ =50

Three mmol of a solution of Template A (5.33 grams, 0.562 mmol OH⁻ /g)is mixed with 1.2 grams of 1.0 N NaOH and 5.4 grams of water. Sodiumborate decahydrate (0.057 gram) is added to this solution and stirreduntil all of the solids have dissolved. Cabosil M-5 fumed silica (0.92gram) is then added to the solution and the resulting mixture is heatedat 160° C. and rotated at 43 rpm for 6 days. A settled product results,which is filtered, washed, dried and determined by XRD to be SSZ-47.

Example 7 Preparation of High-Silica SSZ-47

2.25 Mmoles of a solution of Template A (4.10 g, 0.572 mmol OH⁻ /g) ismixed with 2.25 gram of 1.0 N NaOH and 5.87 grams of water. Tosoh 390HUA, a very high silica Y zeolite, (0.92 gram) is then added to thesolution. Finally, 0.10 gram of zinc acetate dihydrate is dissolved inthe mixture. The resulting mixture is heated at 160° C. for 14 days with43 RPM agitation. The resulting settled product is filtered, washed anddried and determined by XRD to be SSZ-47. The crystallites are quitesmall and the XRD diffraction lines are quite broadened.

Example 8

A reaction is run as in Example 3, except that the template used isTemplate B. The resulting product is SSZ-47.

Example 9 Calcination of SSZ-47

The material from Example 3 is calcined in the following manner. A thinbed of material is heated in a muffle furnace from room temperature to120° C. at a rate of 1° C. per minute and held at 120° C. for threehours. The temperature is then ramped up to 540° C. at the same rate andheld at this temperature for 5 hours, after which it is increased to594° C. and held there for another 5 hours. A 50/50 mixture of air andnitrogen is passed over the zeolite at a rate of 20 standard cubic feetper minute during heating. The X-ray diffraction data for the product isprovided in Table IV below.

                  TABLE IV                                                        ______________________________________                                        2 Theta         d      I/I.sub.0 × 100                                  ______________________________________                                        8.0             11.0   52                                                     9.6             9.19   14                                                     13.0            6.81   16                                                     14.85(Sh)       5.96   4                                                      15.25           5.80   10                                                     16.0            5.54   2                                                      19.25           4.61   57                                                     20.65           4.30   100                                                    22.35           3.97   48                                                     24.05           3.70   19                                                     24.85           3.58   3                                                      26.1            3.41   12                                                     26.7            3.33   16                                                     27.35           3.26   45                                                     27.55(Sh)       3.24   21                                                     29.05           3.07   5                                                      29.8            2.99   4                                                      33.35           2.69   4                                                      35.75           2.51   9                                                      36.65           2.45   2                                                      37.65           2.39   4                                                      39.0            2.31   3                                                      39.5            2.28   2                                                      ______________________________________                                    

Example 10 Calcination of B-SSZ-47

The procedure described in Example 9 is followed on the product fromExample 6, with the exception that the calcination was performed under anitrogen atmosphere.

Example 11 N₂ Micropore Volume

The product of Example 9 is subjected to a surface area and microporevolume analysis using N₂ as adsorbate and via the BET method. Thesurface area of the zeolitic material is 200 M² /g and the microporevolume is 0.06 cc/g, thus exhibiting considerable void volume.

Example 12 NH₄ Exchange

Ion exchange of calcined SSZ-47 material (prepared in Example 9) isperformed using NH₄ NO₃ to convert the zeolite from its Na⁺ form to theNH₄ ⁺ form, and, ultimately, the H⁺ form. Typically, the same mass ofNH₄ NO₃ as zeolite is slurried in water at a ratio of 25-50:1 water tozeolite. The exchange solution is heated at 95° C. for 2 hours and thenfiltered. This procedure can be repeated up to three times. Followingthe final exchange, the zeolite is washed several times with water anddried. This NH₄ ⁺ form of SSZ-47 can then be converted to the H⁺ form bycalcination (as described in Example 9) to 540° C.

Example 13 NH₄ Exchange of B-SSZ-47

The procedure described in Example 12 for ion exchange is followed withthe exception that NH₄ OAc (ammonium acetate) is used in place of theNH₄ NO₃.

Example 14 Constraint Index Determination

The hydrogen form of the zeolite of Example 3 (after treatment accordingto Examples 9 and 12) is pelletized at 2-3 KPSI, crushed and meshed to20-40, and then >0.50 gram is calcined at about 540° C. in air for fourhours and cooled in a desiccator. 0.50 Gram is packed into a 3/8 inchstainless steel tube with alundum on both sides of the zeolite bed. ALindburg furnace is used to heat the reactor tube. Helium is introducedinto the reactor tube at 10 cc/min. and at atmospheric pressure. Thereactor is heated to about 315° C., and a 50/50 (w/w) feed of n-hexaneand 3-methylpentane is introduced into the reactor at a rate of 8μl/min. Feed delivery is made via a Brownlee pump. Direct sampling intoa gas chromatograph begins after 10 minutes of feed introduction. TheConstraint Index value is calculated from the gas chromatographic datausing methods known in the art, and is found to be 1.33. At 315° C. and10 minutes on-stream, feed conversion was greater than 40%.

It can be seen that SSZ-47 has very high cracking activity, indicativeof strongly acidic sites. In addition, the low fouling rate indicatesthat this catalyst has good stability. The C.I. of 1.33 shows almost nopreference for cracking the branched alkane (3-methylpentane) over thelinear n-hexane, which is behavior typical of large-pore zeolites.

Example 15 Use of SSZ-47 To Convert Methanol

The hydrogen form of the zeolite of Example 3 (after treatment accordingto Examples 9 and 12) is pelletized at 2-3 KPSI, then crushed and meshedto 20-40. 0.50 Gram is loaded into a 3/8 inch stainless steel reactortube with alundum on the side of the zeolite bed where the feed isintroduced. The reactor is heated in a Lindberg furnace to 1000° F. for3 hours in air, and then the temperature is reduced to 330° C. in astream of nitrogen at 20 cc/min. A 22.1% methanol feed (22.1 gmethanol/77.9 g water) is introduced into the reactor at a rate of 1.31cc/hr.

SSZ-47 makes considerable light gas and produces considerable liquidproduct under these conditions. A large proportion of product is due tothe formation of durenes, penta- and hexamethylbenzene. Formation ofpenta- and hexamethylbenzene is again indicative of a large porezeolite, as the equilibrium diameter of the latter is 7.1 Angstroms(Chang, C. D., "Methanol to Hydrocarbons", Marcel Dekker, 1983). At 10minutes on stream, the conversion is 100% and the product is rich inpropylene, isobutane and penta- and hexamethylbenzene. The high quantityof isobutane indicates a high rate of hydrogen transfer. The catalystfouls fairly rapidly, giving a low conversion after two hours.

What is claimed is:
 1. A zeolite having a composition, as synthesizedand in the anhydrous state, in terms of mole ratios as follows: ##EQU2##wherein Y is silicon, germanium or a mixture thereof; W is aluminum,gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; cis 1 or 2; d is 2 when c is 1 or d is 3 or 5 when c is 2; M is an alkalimetal cation, alkaline earth metal cation or mixtures thereof; n is thevalence of M; and Q is at least one bicyclo ammonium cation, and havingthe X-ray diffraction lines of Table I.
 2. A zeolite according to claim1 wherein W is aluminum and Y is silicon.
 3. A zeolite according toclaim 1 wherein W is boron and Y is silicon.
 4. A zeolite according toclaim 1 wherein Q has the following structure: ##STR3##
 5. A method ofpreparing a crystalline material having, after calcination, the X-raydiffraction lines of table II, said crystalline material comprising anoxide of a first tetravalent element, trivalent element, pentavalentelement or mixture thereof and an oxide of a second tetravalent elementwhich is different from said first tetravalent element, trivalentelement, pentavalent element or mixture thereof, said method comprisingcontacting under crystallization conditions sources of said oxides and atemplating agent comprising a bicyclo ammonium cation, wherein thetemplating agent has the following structure:
 6. The method according toclaim 5 wherein the first tetravalent element is selected from the groupconsisting of silicon, germanium and combinations thereof.
 7. The methodaccording to claim 5 wherein the second tetravalent element, trivalentelement or pentavalent element is selected from the group consisting ofaluminum, gallium, iron, boron, titanium, indium, vanadium andcombinations thereof.
 8. The method according to claim 7 wherein thesecond tetravalent element or trivalent element is selected from thegroup consisting of aluminum, boron, titanium and combinations thereof.9. The method according to claim 8 wherein the first tetravalent elementis silicon.